Patent GB-1213665-A (GB)
Title: Nitrogen-containing compositions and polymers and process for making same
IPC: C07C275/28
Filed: 1967-11-03
Abstract: 1,213,665. Nitrogen-containing compositions and processes for their preparation. SINCLAIR RESEARCH Inc. 3 Nov., 1967 [7 Nov., 1966], No. 50100/67. Heading C2C. [Also in Division C3] Organic compounds containing either at least one radical -NH-CO- or at least one radical -CO-NH-O-X-, wherein X is selected from -CO-, -SO- and -CO-CO-, e.g. monomeric and polymeric hydroxamates, ureas and urethanes, some of which are claimed to be novel, are obtained by reacting at least one nucleophilic compound having at least one active hydrogen atom with a cyclic nitrile adduct compound of the formula wherein R is a hydrocarbon radical free of nucleophilic groups which may be substituted by non-nucleophilic substituent atoms or groups and n is 1 to 4, said reaction being conducted at a temperature sufficient to effect either (A) a condensation-rearrangement reaction between the nucleophilic compound and the cyclic nitrile adduct compound by which there is formed the uniting radical -NH-CO- wherein the third bond of the nitrogen atom is attached to the residue of the cyclic nitrile adduct compound after removal of the cyclic nitrile adduct group and the fourth bond of the carbon atom is attached to the residue of the nucleophilic compound after removal of the active hydrogen atom, an elimination product of said reaction being CO 2  when X is -CO-, SO 2  when X is -SO- and CO 2  and CO when X is -CO-CO-, or (B) an addition reaction between the nucleophilic compound and the cyclic nitrile adduct compound by which there is formed the uniting radical wherein the fourth bond of the carbon atom is attached to the residue of the cyclic nitrile adduct compound after removal of the cyclic nitrile group and the remaining valence of X is attached to the residue of the nucleophilic compound after removal of an active hydrogen atom. The active hydrogen in the nucleophilic compound may be in the form of -OH, -NH-, -NH 2 , -SH, -SO 2 NH 2 , -SO 2 OH, -COOH, -CSNH 2  or -CONHR groups; when relatively weak nucleophiles are employed the reaction may be catalysed by use of relatively stronger nucleophiles associated with a metal cation or ammonium ion or relatively stronger nucleophiles which neither contain active hydrogen nor are associated with a metal cation or ammonium ion, e.g. tertiary amines. The reaction may be effected to produce hydroxamate derivatives (Type I products) or through or from these hydroxamate compounds (by the elimination of CO 2 , SO 2 , or CO) a variety of compounds (Type II products) such as urethane, urea or ureaurethane groups or linkage-containing organic products. The reaction is generally carried out in the presence or absence of a catalyst at temperatures below the degradation temperature of the desired product; the use of weak base catalysts, such as tertiary amines, having a pKa of up to 8 and relatively low reaction temperatures, e.g. -20‹ to 150‹ C, favours the formation of the hydroxamate compounds (Type I compounds), while the use of strong base catalysts having a pKa value greater than 8 and elevated reaction temperatures, e.g. 30-170‹ C. favours the formation of the Type II products. The type II products may be obtained from the hydroxamates (Type I products), for example, by heating to 50-150‹ C., which decomposition results in the corresponding isocyanate and nucleophilic reactant which may react to provide the Type II products, or alternatively the isocyanates may be isolated. The radical R in the cyclic nitrile adduct starting material may be a monomeric or polymeric hydrocarbon structure containing up to 5000 carbon atoms and may contain heteroatoms as part of the main chain or in side chains. The nucleophiles employed as starting materials may be simple, low molecular weight compounds or polymeric materials and they may be mono- or polyfunctional. Examples of classes of nucleophiles which may be employed are: organic compounds with active hydrogen attached to oxygen or sulphur which include aliphatic, aromatic and mixed aliphatic-aromatic monohydric and polyhydric alohols and thiols, mono- and poly-carboxylic acids and thioacids, sulphonic acids, hydroxyl-containing mono- and polyesters and hydroxy, thio, acid and thioacid-terminated polymeric materials; organic compounds with active hydrogen attached to nitrogen which include aliphatic and aromatic mono- and poly-amines, amides, thioamides, imines and imides, and amine and imine-terminated polymeric materials; organic compounds containing active hydrogen atoms attached to both oxygen and nitrogen atoms which include amino alcohols, imino alcohols amino carboxylic acids and imino acids; nucleophilic compounds associated with a metal cation or ammonium ion which include alkaline metal and ammonium salts of fatty acids and polycarboxylic acids, Grignard reagents, alkoxides, phenates, alkali metal and ammonium amides and imides and organometallic compounds. The novel hydroxamate derivatives which may be prepared by the process of the invention correspond to the formulae wherein R<SP>1</SP> is the same as R defined above, X is -CO-, -SO- or -CO-CO- x is an integer of 1-3, Z is hydrogen, a metal cation or ammonium ion, B is an oxygen, nitrogen, sulphur or carbon atom, Q is a monomeric or polymeric hydrocarbon radical (optionally including heteroatoms) having a molecular weight of at least 14 which may be substituted by non-nucleophilic substituent atoms or groups, x<SP>1</SP> is an integer of at least 1 up to the functionality of Q, R<SP>11</SP> is hydrogen or Q, a<SP>1</SP> and a<SP>11</SP> are 0 or 1 with the proviso that when B is oxygen or sulphur n<SP>1</SP> and n<SP>11</SP> are each 0, and when B is nitrogen or carbon n<SP>1</SP> is 1 and n<SP>11</SP> is either 0 or 1 respectively, m is an integer greater than 0, p is an integer of 1-3, and the radical represents the same or different residues of the nucleophile after the removal of Z. Novel type II products of the invention correspond to the formulae wherein the symbols are as above-defined. The invention also includes storage-stable compositions comprising the cyclic nitrile adduct reactant, the cyclic nitrile-terminated type II products of the formula VII, the cyclic nitrile adduct group-terminated hydroxamate compounds of the formula III or mixtures thereof with a nucleophilic compound as defined above which is non-reactive at ambient temperatures with the said nitrogen-containing material; the compositions may also contain other conventional additives.